CN105121508A - Novel polycarboxylic acid anhydride and use thereof - Google Patents

Novel polycarboxylic acid anhydride and use thereof Download PDF

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Publication number
CN105121508A
CN105121508A CN201480022252.2A CN201480022252A CN105121508A CN 105121508 A CN105121508 A CN 105121508A CN 201480022252 A CN201480022252 A CN 201480022252A CN 105121508 A CN105121508 A CN 105121508A
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polycarboxylic acid
acid anhydride
general formula
formula
substituent
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CN105121508B (en
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吉川秀幸
永岛田贵之
山崎舞子
原田依里子
辻泰树
山中正彦
山崎太郎
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New Japan Chemical Co Ltd
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New Japan Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)

Abstract

The present invention relates to a polycarboxylic acid anhydride containing a structural unit represented by general formula (1). According to the present invention, a novel polycarboxylic acid anhydride is provided. When the polycarboxylic acid anhydride is used as a curing agent for, for example, an epoxy resin, the mixing balance in the resultant resin composition can be stabilized. Therefore, a resin molded article having excellent heat resistance, transparency, thermal yellowish discoloration resistance, surface hardness, solvent resistance, flexibility and adhesiveness can be provided using the polycarboxylic acid anhydride.

Description

Novel polycarboxylic acid anhydride and uses thereof
Technical field
The present invention relates to a kind of novel polycarboxylic acid anhydride and uses thereof.
Background technology
Carboxylic acid anhydride is not only useful compound as the starting material of organic synthesis, and as the raw material of Synolac, unsaturated polyester resin, polyamide resin, polyimide resin, photoresist etc. or its properties-correcting agent; The solidifying agent of epoxy resin etc. are also useful compounds.Further, carboxylic acid anhydride is widely used as the starting material in the various fields such as tackiness agent, coating, ink, toning agent, coating-forming agent, shaped material, electrically insulating material, semiconductor-encapsulating material, anticorrosive additive material, softening agent, lubricating oil, fibre finish, tensio-active agent, medicine, agricultural chemicals, resin additive or resin curing agent.
Particularly the cyclic carboxylic acids acid anhydride such as Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenating methyl carbic anhydride has following feature: as epoxy curing agent, contraction during the excellent and resin solidification of Combination is little, the excellent size stability of therefore obtained epoxy resin molding (cured article).
In addition, compared with the epoxy curing agent of amine system, the storage period of the epoxy curing agent containing this cyclic carboxylic acids acid anhydride is long, and, with use compared with the epoxy curing agent of amine system and the cured article that obtains, use this cyclic carboxylic acids acid anhydride and the resin cured matter obtained has the such advantage of the transparency, high-temperature electric characteristic good, be therefore used as electronic unit by injection moulding, impregnation, the stacked and sealing material (patent documentation 1 and non-patent literature 1) of the insulating material obtained and photosemiconductor.
But, when use this cyclic carboxylic acids acid anhydride epoxy resin is heating and curing, this cyclic carboxylic acids acid anhydride self because of heating volatilize, therefore cause the pollution of heating unit, operating environment remarkable deterioration and become problem.In addition, there is following problem: a part of acid anhydrides loss like this in resin combination, the complex equilibrium of resin combination is disintegrated thus, cannot obtain desired solidification physical property.Particularly, when manufacturing film, small molding, the impact that the physical property of acid anhydrides on cured article of volatilizing during being heating and curing of resin is brought is large, is difficult to the transparency, thermotolerance etc. that obtain resin, therefore requires to develop nonvolatile acid anhydrides (non-volatile acid anhydrides).The volatilization of the acid anhydrides when being heating and curing of resin is like this because of caused by the high vapour pressure of acid anhydrides self.
Therefore, have developed chain (non-annularity) polycarboxylic acid anhydride formed by the polycondensation of polycarboxylic acid and replace cyclic carboxylic acids acid anhydride.Such as, be used as the solidifying agent of the thermosetting resins such as epoxy resin, melamine resin, acrylic acid or the like powder coating by the chain polycarboxylic acid anhydride making the aliphatic dicarboxylic acid such as poly-nonane diacid, poly-sebacic acid obtain at intermolecular generation dehydration condensation all the time, when using this chain polycarboxylic acid anhydride as solidifying agent, easily obtain pliability and the excellent cured article of resistance to sudden heating, the solidifying agent therefore as powder coating, resin for injection is useful compound (patent documentation 2).
In addition, it is useful for Patent Document 3 discloses the compound represented by following general formula (I) at least with two non-annularity acid anhydrides as the linking agent (solidifying agent) of epoxy resin.
(in formula, R represents the monovalent hydrocarbon of carbonatoms 2 ~ 50, and R ' represents the bivalent hydrocarbon radical of carbonatoms 2 ~ 50.In addition, the alkyl represented by R and R ' can contain ehter bond, urethane bond or ester bond.N is the integer of 1 ~ 500.)
But, in patent documentation 3, the concrete compound recorded is by Tetra hydro Phthalic anhydride and 1, the chain petchem (compound of embodiment 7) that 6-hexylene glycol obtains, this compound has aromatic nucleus, therefore there are the following problems: its cured article easily occurs painted, and the second-order transition temperature (Tg) as the index of thermotolerance is very low.
So, although have developed non-annularity acid anhydrides, when using these acid anhydrides as resin curing agent, still there is various problem in the resin molded body obtained, and present situation does not also obtain excellent resin molded body.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2008-81514 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2010-106226 publication
Patent documentation 3: No. 93/011188th, International Publication
Non-patent literature
Non-patent literature 1: Epoxy Resin Technology association compiles " introduction epoxy resin basis section I " (" Gross says エ Port キ シ Trees fat base Foundation Knitting I "), first edition, the 1st volume, Epoxy Resin Technology association, on November 19th, 2003, p.156-174
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide a kind of novel polycarboxylic acid anhydride and the resin curing agent containing this polycarboxylic acid anhydride.
In addition, the object of the present invention is to provide the resin molded body that a kind of thermotolerance, the transparency, heat-resisting xanthochromia, surface hardness, solvent resistance, resistance to bend(ing) and adherence (adherence) are excellent.
For the method for dealing with problems
The present inventors is studied repeatedly in order to solve the problem, and found that a kind of novel polycarboxylic acid anhydride.In addition, find that novel polycarboxylic acid anhydride of the present invention is engaged in resin the resin molded body that said composition is solidified solves above-mentioned problem, thus complete the present invention.
That is, the invention provides following polycarboxylic acid anhydride, its manufacture method and uses thereof etc.
Item 1.
A kind of polycarboxylic acid anhydride, it contains the structural unit represented by general formula (1).
(in formula, Rx represents cycloalkylidene (シ Network ロ ア Le キ レ Application base) or more than 2 cycloalkylidenes group via singly-bound or divalent group bonding, and at this, this cycloalkylidene can have substituting group.
R 1~ R 10identical or different, represent hydrogen atom respectively or substituent alkyl can be had.R 1~ R 10among, two groups can form divalent group by bonding mutually.)
Item 2.
Polycarboxylic acid anhydride as described in item 1, wherein, the divalent group of Rx represented by general formula (2).
(in formula, W 1and W 2identical or different, expression can have substituent cycloalkylidene, L 1represent singly-bound, substituent alkylidene group can be had, substituent cycloalkylidene can be had, substituent ring alkylidene can be had (シ Network ロ ア Le キ リ デ Application base) ,-O-,-S-,-CO-,-SO-or-SO 2-.N represents the integer of 0 or 1.Wavy line represents bonding position.)
Item 3.
Polycarboxylic acid anhydride as described in item 2, wherein, W 1and W 2identical or different, be selected from the divalent group represented by following general formula (a) or (b).
(in formula, R 11and R 12identical or different, represent respectively and can have substituent alkyl or substituent cycloalkyl can be had.
O represents the integer of 0 ~ 8, when o represents 2 ~ 8, and 2 ~ 8 R 11can be the same or different.When o represents 2 ~ 8,2 R 11mutually can form divalent group by bonding.
P represents the integer of 0 ~ 12, when p represents 2 ~ 12, and 2 ~ 12 R 12can be the same or different.When p represents 2 ~ 12,2 R 12mutually can form divalent group by bonding.Wavy line represents bonding position.)
Item 4.
Polycarboxylic acid anhydride as described in item 1, wherein, the compound of the polycarboxylic acid anhydride containing the structural unit represented by general formula (1) represented by general formula (3).
(in formula, Rx and R 1~ R 10same as described above.R 13expression can have substituent alkyl or can have substituent cycloalkyl.X represents more than 2.)
Item 5.
Polycarboxylic acid anhydride as described in item 1, its number-average molecular weight (polystyrene conversion) is 500 ~ 6000.
Item 6.
Polycarboxylic acid anhydride as described in item 1, it is at 1800cm -1~ 1825cm -1place has characteristic infrared absorption spectrum.
Item 7.
A manufacture method for polycarboxylic acid anhydride described in item 1, it possesses the step of carrying out condensation reaction in the reaction solution containing the compound represented by general formula (4).
(in formula, Rx and R 1~ R 10same as described above.)
Item 8.
A kind of polycarboxylic acid anhydride, it is obtained by the manufacture method described in item 7.
Item 9.
A kind of polycarboxylic acid anhydride, it contains the structural unit represented by general formula (1) and the structural unit represented by general formula (5).
(in formula, Rx represents cycloalkylidene or more than 2 cycloalkylidenes group via singly-bound or divalent group bonding, and at this, this cycloalkylidene can have substituting group.
R 1~ R 10identical or different, represent hydrogen atom respectively or substituent alkyl can be had.R 1~ R 10among, two groups can form divalent group by bonding mutually.)
(in formula, R 14identical or different, represent respectively and can have substituent alkyl or substituent cycloalkyl can be had.
R represents the integer of 0 ~ 8, when r represents 2 ~ 8, and 2 ~ 8 R 14can be the same or different.When r is 2 ~ 8,2 R 14mutually can form divalent group by bonding.)
Item 10.
Polycarboxylic acid anhydride as described in item 9, wherein, the divalent group of Rx represented by general formula (2).
(in formula, W 1and W 2identical or different, expression can have substituent cycloalkylidene, L 1represent singly-bound, substituent alkylidene group can be had, substituent cycloalkylidene can be had, substituent ring alkylidene ,-O-,-S-,-CO-,-SO-or-SO can be had 2-.N represents the integer of 0 or 1.Wavy line represents bonding position.)
Item 11.
Polycarboxylic acid anhydride as described in item 9, wherein, the ratio of the structural unit represented by general formula (1) and the structural unit represented by general formula (5) is the scope of the mol ratio of 99.9:0.1 ~ 30:70.
Item 12.
Polycarboxylic acid anhydride as described in item 11, wherein, the ratio of the structural unit represented by general formula (1) and the structural unit represented by general formula (5) is the scope of the mol ratio of 90:10 ~ 45:55.
Item 13.
Polycarboxylic acid anhydride as described in item 9, wherein, W 1and W 2identical or different, be selected from the divalent group represented by following general formula (a) or (b).
(in formula, R 11and R 12identical or different, represent respectively and can have substituent alkyl or substituent cycloalkyl can be had.
O represents the integer of 0 ~ 8, when o represents 2 ~ 8, and 2 ~ 8 R 11can be the same or different.When o represents 2 ~ 8,2 R 11mutually can form divalent group by bonding.
P represents the integer of 0 ~ 12, when p represents 2 ~ 12, and 2 ~ 12 R 12can be the same or different.When p represents 2 ~ 12,2 R 12mutually can form divalent group by bonding.Wavy line represents bonding position.)
Item 14.
Polycarboxylic acid anhydride as described in item 9, wherein, the compound of polycarboxylic acid anhydride represented by general formula (6) containing the structural unit represented by general formula (1) and the structural unit represented by general formula (5).
(in formula, Rx, R 1~ R 10, R 14same as described above with r.R 13expression can have substituent alkyl or can have substituent cycloalkyl.X represents that more than 1, y represents that more than 1, x+y represents more than 2.The arrangement of each unit of x and y is not defined in the order of above-mentioned arrangement.)
Item 15.
Polycarboxylic acid anhydride as described in item 9, its number-average molecular weight (polystyrene conversion) is 500 ~ 6000.
Item 16.
Polycarboxylic acid anhydride as described in item 9, it is at 1800cm -1~ 1825cm -1place has characteristic infrared absorption spectrum.
Item 17.
A manufacture method for polycarboxylic acid anhydride described in item 9, it possesses the step of carrying out condensation reaction in the reaction solution containing the compound represented by general formula (4) and the cyclohexane cyclohexanedimethanodibasic compound represented by general formula (7).
(in formula, Rx and R 1~ R 10same as described above.)
(in formula, R 14same as described above with r.)
Item 18.
The manufacture method of the polycarboxylic acid anhydride as described in item 9, wherein, the interpolation mol ratio of the compound represented by general formula (4) and the cyclohexane cyclohexanedimethanodibasic compound represented by general formula (7) is the scope of 99.9:0.1 ~ 30:70.
Item 19.
The manufacture method of the polycarboxylic acid anhydride as described in item 18, wherein, the interpolation mol ratio of the compound represented by general formula (4) and the cyclohexane cyclohexanedimethanodibasic compound represented by general formula (7) is the scope of 90:10 ~ 45:55.
Item 20.
A kind of polycarboxylic acid anhydride, it is obtained by the manufacture method described in item 19.
Item 21.
A kind of epoxy curing agent, it contains the polycarboxylic acid anhydride described in any one be selected from item 1 ~ 6,8 ~ 16 and 18 ~ 20.
Item 22.
A kind of composition, it contains epoxy curing agent, (b) epoxy resin and (c) curing catalyst described in (a) item 21.
Item 23.
A kind of molding, it obtains by making the composition described in item 22 solidify.
Item 24.
A formation method for film, is characterized in that, is coated on matrix, makes curing of coating by the composition described in item 22, thus formation thickness is the film of below 1mm.
Item 25.
A kind of film, it makes the thickness that the composition described in item 22 solidifies be the film of below 1mm.
Item 26.
Film as described in item 25, this film is indicating meter coated material.
Invention effect
According to the present invention, novel polycarboxylic acid anhydride and the resin curing agent containing this polycarboxylic acid anhydride can be provided.In addition, when being engaged in by this polycarboxylic acid anhydride in resin and make said composition solidify, the resin molded body with excellent thermotolerance, the transparency, heat-resisting xanthochromia, surface hardness, solvent resistance, resistance to bend(ing) and adherence can be obtained.
Accompanying drawing explanation
Fig. 1 is infrared absorption spectrum that the is polycarboxylic acid anhydride solution obtained in embodiment 1 is dry, that distill the polycarboxylic acid anhydride obtained after removing desolventizing.
Fig. 2 is infrared absorption spectrum that the is polycarboxylic acid anhydride solution obtained in embodiment 2 is dry, that distill the polycarboxylic acid anhydride obtained after removing desolventizing.
Fig. 3 is infrared absorption spectrum that the is polycarboxylic acid anhydride solution obtained in embodiment 3 is dry, that distill the polycarboxylic acid anhydride obtained after removing desolventizing.
Fig. 4 is infrared absorption spectrum that the is polycarboxylic acid anhydride solution obtained in embodiment 4 is dry, that distill the polycarboxylic acid anhydride obtained after removing desolventizing.
Fig. 5 is infrared absorption spectrum that the is polycarboxylic acid anhydride solution obtained in embodiment 5 is dry, that distill the polycarboxylic acid anhydride obtained after removing desolventizing.
Fig. 6 is infrared absorption spectrum that the is polycarboxylic acid anhydride solution obtained in embodiment 6 is dry, that distill the polycarboxylic acid anhydride obtained after removing desolventizing.
Fig. 7 is infrared absorption spectrum that the is polycarboxylic acid anhydride solution obtained in embodiment 7 is dry, that distill the polycarboxylic acid anhydride obtained after removing desolventizing.
Fig. 8 is infrared absorption spectrum that the is polycarboxylic acid anhydride solution obtained in embodiment 9 is dry, that distill the polycarboxylic acid anhydride obtained after removing desolventizing.
Embodiment
Below, novel polycarboxylic acid anhydride of the present invention, its manufacture method and uses thereof are described particularly.
In this manual, the statement about " containing " comprises " containing ", " in fact only by ... form " and " only by ... form " concept.
1. polycarboxylic acid anhydride
The compound of polycarboxylic acid anhydride of the present invention represented by following (1-1) or (1-2).Below, sometimes also the compound represented by (1-1) is called " two composition systems polycarboxylic acid anhydride ", the compound represented by following (1-2) is called " three component system polycarboxylic acid anhydride ".
(1-1) two composition systems polycarboxylic acid anhydride
Of the present invention pair of composition system polycarboxylic acid anhydride for carrying out condensation reaction and the compound obtained in the reaction solution comprising the polycarboxylic acid anhydride containing the structural unit represented by general formula (4).
(in formula, Rx represents cycloalkylidene or more than 2 cycloalkylidenes group via singly-bound or divalent group bonding, and at this, this cycloalkylidene has or do not have substituting group.
R 1~ R 10identical or different, represent hydrogen atom respectively or have or not there is substituent alkyl.R 1~ R 10among, two groups can form divalent group by bonding mutually.)
As the of the present invention pair of composition system polycarboxylic acid anhydride so obtained, such as, the polycarboxylic acid anhydride containing the structural unit represented by general formula (1) can be exemplified.
(in formula, Rx and R 1~ R 10same as described above.)
As the Rx in general formula (4) or general formula (1), for cycloalkylidene or more than 2 cycloalkylidenes are via the group of singly-bound or divalent group bonding, such as, as Rx, the divalent group represented by following general formula (2) can be enumerated.
(in formula, W 1and W 2identical or different, represent and have or not there is substituent cycloalkylidene, L 1represent singly-bound, have or not there is substituent alkylidene group, have or not there is substituent cycloalkylidene, there is or do not have substituent ring alkylidene ,-O-,-S-,-CO-,-SO-or-SO 2-.N represents the integer of 0 or 1.Wavy line represents bonding position.)
Specifically, when the divalent group of Rx represented by above-mentioned general formula (2), of the present invention pair of composition system polycarboxylic acid anhydride for carrying out condensation reaction and the compound obtained in the reaction solution containing the compound represented by general formula (8).
(in formula, W 1, W 2, L 1, n and R 1~ R 10same as described above.)
As the two composition systems polycarboxylic acid anhydride so obtained, the compound containing the structural unit represented by general formula (9) can be enumerated.
(in formula, W 1, W 2, L 1, n and R 1~ R 10same as described above.)
Polycarboxylic acid anhydride containing above-mentioned general formula (1) or the structural unit represented by general formula (9) of the present invention can be set forth in the compound that two ends have carboxyl (-COOH), the compound after the group of hydrogen atom represented by general formula (10) being preferably in the carboxyl of two ends of polycarboxylic acid anhydride of the present invention replaces.
(in formula, R 13represent and there is or do not have substituent alkyl or have or not there is substituent cycloalkyl.* bonding position is represented.)
As its concrete example, the compound represented by general formula (3) or the compound represented by general formula (11) can be enumerated.
(in formula, Rx, R 1~ R 10and R 13same as described above.X represents more than 2.)
(in formula, W 1, W 2, L 1, n, R 1~ R 10, R 13same as described above with x.)
Described in each group represented in above-mentioned general formula (1) ~ (4) and (8) ~ (11) is specific as follows.
As Rx, W 1and W 2in cycloalkylidene be not particularly limited, such as, the cycloalkylidene of carbonatoms 3 ~ 50 can be enumerated.Specifically, the monocyclic cycloalkylidenes such as cyclopropylidene, sub-cyclobutyl, cyclopentylidene, cyclohexylidene can be enumerated; 7-oxabicyclo [2,2,1] sub-heptyl (7-オ キ サ PVC シ Network ロ [2,2,1] へ プ チ レ Application base), the polycycle cycloalkylidene such as decahydro naphthyl (hydrogenation naphthyl), sub-norborneol alkyl (ノ Le ボ Le ニ レ Application base), sub-adamantyl (ア ダ マ Application チ レ Application base).At this, this cycloalkylidene can have the substituting groups such as 1 ~ 8 alkyl, cycloalkyl, halogen atom further.
As Rx, W 1and W 2in cycloalkylidene, be preferably following general formula (a) or the divalent group represented by (b).
(in formula, R 11and R 12identical or different, represent respectively and there is or do not have substituent alkyl or have or not there is substituent cycloalkyl.
O represents the integer of 0 ~ 8, when o represents 2 ~ 8, and 2 ~ 8 R 11can be the same or different.When o represents 2 ~ 8,2 R 11mutually can form divalent group by bonding.
P represents the integer of 0 ~ 12, when p represents 2 ~ 12, and 2 ~ 12 R 12can be the same or different.When p represents 2 ~ 12,2 R 12mutually can form divalent group by bonding.Wavy line represents bonding position.)
As the cycloalkylidene represented by above-mentioned formula (a), be more preferably the divalent group represented by following formula (a-1) ~ (a-8).
(in formula, wavy line is same as described above.)
As the decahydro naphthyl represented by above-mentioned formula (b), 2 represented by following formula (b-1) can be exemplified, 7-decahydro naphthyl, 2 represented by formula (b-2), 6-decahydro naphthyl, 1 represented by formula (b-3), 6-decahydro naphthyl, 1 represented by formula (b-4), 7-decahydro naphthyl, 1 represented by formula (b-5), 8-decahydro naphthyl and 1 represented by formula (b-6), divalent group represented by 5-decahydro naphthyl, represented by the formula (b-1) 2 of being preferably, 7-decahydro naphthyl or 2,6-decahydro naphthyls represented by formula (b-2).
(in formula, R 12, p and wavy line same as described above.)
As the divalent group represented by above-mentioned formula (b), be more preferably following formula (b-1-1) or the divalent group represented by (b-2-1).
(in formula, wavy line is same as described above.)
In this manual, when indicating wavy line in divalent group, it is towards being not particularly limited, both can be this record towards also can for upset after towards.
It should be noted that, Rx, W 1and W 2in cycloalkylidene or more than 2 cycloalkylidenes in Rx can remove the group after two hydroxyls in other words as from naphthenic hydrocarbon glycol via the group of singly-bound or divalent group bonding.
Remove the group after two hydroxyls as from naphthenic hydrocarbon glycol, such as, can enumerate from 1,2-ring propylene glycol, 1,2-cyclobutanediol, 1,3-cyclobutanediol, 1,2-ring pentanediol, 1,3-ring pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1, the monocyclic naphthenic hydrocarbon glycol such as 2-ring heptanediol, 1,3-ring heptanediol, Isosorbide-5-Nitrae-ring heptanediol remove the group after two hydroxyls; The group after two hydroxyls is removed from polycycle naphthenic hydrocarbon glycol such as A Hydrogenated Bisphenol A class such as norbornylene (ノ Le ボ Le ネ Application), dicyclopentadiene glycol (ジ シ Network mouth ペ Application タ ジ エ Application ジ オ ー Le) class, diamantane glycols, hydrogenated naphthalene glycols, hydrogenated biphenyl glycols, Hydrogenated Bisphenol A, A Hydrogenated Bisphenol A C, A Hydrogenated Bisphenol A E, A Hydrogenated Bisphenol A F, A Hydrogenated Bisphenol A Z.Among these, preferably remove the group after two hydroxyls from Isosorbide-5-Nitrae-cyclohexanediol, hydrogenated naphthalene glycols or A Hydrogenated Bisphenol A class.
As the L in general formula (2), (8), (9) and (11) 1, singly-bound can be enumerated, have or not there is substituent alkylidene group, have or not there is substituent cycloalkylidene, there is or do not have substituent ring alkylidene ,-O-,-S-,-CO-,-SO-or-SO 2-represented divalent group.
At this, as L 1the represented alkylidene group or do not have with substituent alkylidene group, is not particularly limited, such as, can enumerates the alkylidene group of the carbonatoms 1 ~ 10 of straight-chain.Be preferably the alkylidene group of the straight-chain carbonatomss 1 ~ 6 such as methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, be more preferably methylene radical.
As this L 1for having or do not have concrete example during substituent methylene radical, the group represented by general formula (c) can be enumerated.
(in formula, R 15and R 16identical or different, the cycloalkyl representing hydrogen atom, the alkyl that can be replaced by halogen atom respectively or can be replaced by halogen atom.Wavy line represents bonding position.)
Among above-mentioned general formula (C), be preferably the divalent group represented by following formula (c-1) ~ (c-8).
(in formula, wavy line represents bonding position.)
In general formula (2), (8), (9) and (11), as L 1the represented cycloalkylidene or do not have with substituent cycloalkylidene, is not particularly limited, such as, can enumerates the cycloalkylidene of carbonatoms 3 ~ 10.Be preferably 1,2-cyclopropane two base, 1,2-tetramethylene two base, 1,2-pentamethylene two base, 1,3-pentamethylene two base, 1,2-hexanaphthene two base, 1,3-hexanaphthene two base, 1, the cycloalkylidene of the carbonatomss 3 ~ 6 such as 4-hexanaphthene two base, is particularly preferably Isosorbide-5-Nitrae-hexanaphthene two base.
In general formula (2), (8), (9) and (11), as L 1the represented ring alkylidene or do not have with substituent ring alkylidene, is not particularly limited, such as, can enumerates the ring alkylidene of carbonatoms 3 ~ 30.As having or do not have substituent ring alkylidene, be preferably ring propylidene base, ring fourth pitches base, ring pitches base, cyclohexylidene base, 3,5 heptan, the ring alkylidene of the carbonatomss 3 ~ 20 such as 5-3-methyl cyclohexanol fork base, be particularly preferably cyclohexylidene base, 3,5,5-3-methyl cyclohexanol fork bases.
As R 1~ R 10the shown alkyl or do not have with substituent alkyl, is not particularly limited, and such as, can enumerate the alkyl of the carbonatoms 1 ~ 10 of straight-chain or branched.Specifically, the alkyl of the carbonatomss 1 ~ 6 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl can be enumerated.Wherein be preferably methyl, ethyl, isobutyl-, the tertiary butyl.This alkyl can have more than 1 substituting group such as cycloalkyl, halogen atom further.
As R 11and R 12the represented alkyl or do not have with substituent alkyl, is not particularly limited, such as, can enumerates the alkyl of the carbonatoms 1 ~ 10 of straight-chain or branched.Specifically, the alkyl of the carbonatomss 1 ~ 6 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl can be enumerated.Wherein be preferably methyl, ethyl, isobutyl-, the tertiary butyl.This alkyl can have more than 1 substituting group such as cycloalkyl, halogen atom further.
As R 11and R 12the represented cycloalkyl or do not have with substituent cycloalkyl, is not particularly limited, such as, can enumerates the cycloalkyl of carbonatoms 3 ~ 30.Specifically, be the monocyclic cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; The polycycle cycloalkyl such as tetralyl (hydrogenation naphthyl), norcamphyl, adamantyl, is particularly preferably cyclohexyl.This cycloalkyl can have the substituting groups such as more than 1 alkyl, cycloalkyl, halogen atom further.
As R 13the represented alkyl or do not have with substituent alkyl, is not particularly limited, such as, can enumerates the alkyl of the carbonatoms 1 ~ 10 of straight-chain or branched.Specifically, the alkyl of the carbonatomss 1 ~ 6 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl can be enumerated.Wherein be preferably methyl, ethyl, isobutyl-, the tertiary butyl.This alkyl can have more than 1 substituting group such as cycloalkyl, halogen atom further.
As R 13the represented cycloalkyl or do not have with substituent cycloalkyl, is not particularly limited, such as, can enumerates the cycloalkyl of carbonatoms 3 ~ 30.Specifically, be the monocyclic cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; The polycycle cycloalkyl such as tetralyl (hydrogenation naphthyl), norcamphyl, adamantyl, is particularly preferably cyclohexyl.This cycloalkyl can have the substituting groups such as more than 1 alkyl, cycloalkyl, halogen atom further.
As R 15and R 16the represented alkyl that can be replaced by halogen atom, is not particularly limited, such as, can enumerates the alkyl that can be replaced by halogen atom of the carbonatoms 1 ~ 10 of straight-chain or branched.Specifically, the alkyl of the unsubstituted carbonatomss 1 ~ 6 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl can be enumerated; The haloalkyl of the carbonatomss 1 ~ 6 such as trifluoromethyl, pentafluoroethyl group, trichloromethyl.Wherein be preferably methyl, ethyl, isobutyl-, trifluoromethyl.
As R 15and R 16the represented cycloalkyl that can be replaced by halogen atom, is not particularly limited, such as, can enumerates the cycloalkyl of carbonatoms 3 ~ 30.Specifically, be the monocyclic cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; The polycycle cycloalkyl such as tetralyl (hydrogenation naphthyl), norcamphyl, adamantyl, is particularly preferably cyclohexyl.This cycloalkyl can have the substituting groups such as more than 1 alkyl, cycloalkyl, halogen atom further.
As the alkyl in this manual alternatively represented by base, such as, can enumerate the alkyl of the carbonatoms 1 ~ 10 of straight-chain or branched.Be preferably the alkyl of the carbonatomss 1 ~ 6 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, be particularly preferably methyl.
As the cycloalkyl in this manual alternatively represented by base, be not particularly limited, such as, the cycloalkyl of carbonatoms 3 ~ 10 can be enumerated.Be preferably the monocyclic cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; The polycycle cycloalkyl such as tetralyl (hydrogenation naphthyl), norcamphyl, adamantyl, is particularly preferably cyclohexyl.
As the halogen atom in this manual alternatively represented by base, such as, fluorine, chlorine, bromine, iodine etc. can be enumerated.Be preferably fluorine or chlorine.
R 1~ R 10among, when two mutual bondings of group form divalent group, as this divalent group, such as, can alkylidene group be enumerated.
R 1~ R 10among, two mutual bondings of group and when there is alkylidene group, specifically, as the group represented by following formula (d), the group etc. represented by following (d-1) can be enumerated.
(in formula, R 1~ R 10same as described above with wavy line.)
(in formula, R 1, R 3~ R 8, R 10same as described above with wavy line.R 17represent and have or not there is substituent alkylidene group.)
At this, as alkylidene group, be not particularly limited, such as, the alkylidene group of the carbonatoms 1 ~ 4 of straight-chain can be enumerated.Be preferably the alkylidene group of the carbonatomss 1 ~ 4 such as methylene radical, ethylidene, propylidene, butylidene, be preferably methylene radical or ethylidene.
Among group represented by above-mentioned formula (d-1), the group particularly preferably represented by following formula (d-1-1), the group represented by formula (d-1-2) and the group represented by formula (d-1-3).
(in formula, wavy line is same as described above.)
In above-mentioned general formula (a), when o represents 2 ~ 8,2 R 11mutually can form divalent group by bonding, as this divalent group, such as, can enumerate and have or not there is substituent alkylidene group.Have as this or not there is substituent alkylidene group, with above-mentioned L 1in the group enumerated identical.
In above-mentioned general formula (b), when p represents 2 ~ 12,2 R 12mutually can form divalent group by bonding, as this divalent group, such as, can enumerate and have or not there is substituent alkylidene group.Have as this or not there is substituent alkylidene group, with above-mentioned L 1in the group enumerated identical.
The two composition systems polycarboxylic acid anhydride so obtained sometimes because of two alcohol radicals or two carboxyls sterie configuration and have the isomer of trans body and cis body, from the viewpoint of making effect of the present invention be played, trans body, cis body and their mixture all can use.
X in general formula (3) and (11) represents the integer of more than 2, is preferably 2 ~ 100, is more preferably 4 ~ 20.X represents the mean number of the unit in polymkeric substance, is tried to achieve by gel permeation chromatography (GPC).
The number-average molecular weight of of the present invention pair of composition system polycarboxylic acid anhydride is preferably the scope of 500 ~ 6000, is more preferably the scope of 2000 ~ 6000.Number-average molecular weight such as can use the known methods such as gel permeation chromatography (GPC) to measure, as polystyrene conversion number-average molecular weight (Mn) and tried to achieve.
As the anhydride equivalent of of the present invention pair of composition system polycarboxylic acid anhydride, be preferably the scope of 300 ~ 5000g/eq, be more preferably the scope of 500 ~ 3000g/eq, be particularly preferably the scope of 600 ~ 1500g/eq.It should be noted that, anhydride equivalent is applied the calculating formula recorded in aftermentioned embodiment and is calculated.
The of the present invention pair of composition system volatility of polycarboxylic acid anhydride in the temperature range in order to make epoxy resin cure usually adopt is extremely low.
Of the present invention pair of composition system polycarboxylic acid anhydride is at 1790cm -1~ 1835cm -1scope in show the characteristic peak coming from anhydride group, particularly at 1800cm -1~ 1825cm -1scope in demonstrate characteristic peak.
(1-2) three component system polycarboxylic acid anhydride
Three component system polycarboxylic acid anhydride of the present invention is the compound carrying out condensation reaction and obtain in the reaction solution containing the compound represented by general formula (4) and general formula (7).
(in formula, Rx and R 1~ R 10same as described above.)
(in formula, R 14identical or different, represent respectively and there is or do not have substituent alkyl or have or not there is substituent cycloalkyl.
R represents the integer of 0 ~ 8, when r represents 2 ~ 8, and 2 ~ 8 R 14can be the same or different.When r is 2 ~ 8,2 R 14mutually can form divalent group by bonding.)
The three component system polycarboxylic acid anhydride so obtained can exemplify the compound containing the structural unit represented by general formula (1) and the structural unit represented by general formula (5).
(in formula, Rx and R 1~ R 10same as described above.)
(in formula, R 14same as described above with r.)
As the Rx in general formula (4) or general formula (1), for cycloalkylidene or more than 2 cycloalkylidenes are via the group of singly-bound or divalent group bonding, such as, as Rx, the divalent group represented by following general formula (2) can be enumerated.
(in formula, W 1, W 2, L 1, n and wavy line same as described above.)
Specifically, when the divalent group of Rx represented by above-mentioned general formula (2), three component system polycarboxylic acid anhydride of the present invention is the compound carrying out condensation reaction and obtain in the reaction solution containing the compound represented by general formula (8) and the cyclohexane cyclohexanedimethanodibasic compound represented by above-mentioned general formula (7).
(in formula, W 1, W 2, L 1, n and R 1~ R 10same as described above.)
The three component system polycarboxylic acid anhydride so obtained can exemplify the compound containing the structural unit represented by general formula (9) and the structural unit represented by general formula (5).
(in formula, W 1, W 2, L 1, n and R 1~ R 10same as described above.)
(in formula, R 14same as described above with r.)
Three component system polycarboxylic acid anhydride of the present invention can be set forth in the compound that two ends have carboxyl (-COOH), the compound after the group of the hydrogen atom being preferably in the carboxyl of two ends of polycarboxylic acid anhydride of the present invention represented by general formula (10) replaces.
(in formula, R 13represent and there is or do not have substituent alkyl or have or not there is substituent cycloalkyl.* bonding position is represented.)
As its concrete example, the compound represented by general formula (6) or the compound represented by general formula (12) can be enumerated.
(in formula, Rx, R 1~ R 10, R 14same as described above with r.R 13represent and there is or do not have substituent alkyl or have or not there is substituent cycloalkyl.X represents that more than 1, y represents that more than 1, x+y represents more than 2.The arrangement of each unit of x and y is not defined in the order of above-mentioned arrangement.)
(in formula, W 1, W 2, L 1, R 1~ R 10, R 13, R 14, r, n, x and y be same as described above.)
Among each group represented in above-mentioned general formula (1), (2), (4) ~ (10) and (12), Rx, R 1~ R 13, W 1, W 2, L 1, identical with group cited in two composition systems polycarboxylic acid anhydride of above-mentioned (1-1) with n.
At this, below the group do not illustrated in above-mentioned (1-1) is described.
As R 14the represented alkyl or do not have with substituent alkyl, is not particularly limited, such as, can enumerates the alkyl of the carbonatoms 1 ~ 10 of straight-chain or branched.Specifically, the alkyl of the carbonatomss 1 ~ 6 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl can be enumerated.Wherein be preferably methyl, ethyl, isobutyl-, the tertiary butyl.This alkyl can have more than 1 substituting group such as cycloalkyl, halogen atom further.
As R 14the represented cycloalkyl or do not have with substituent cycloalkyl, is not particularly limited, such as, can enumerates the cycloalkyl of carbonatoms 3 ~ 30.Specifically, be the monocyclic cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; The polycycle cycloalkyl such as tetralyl (hydrogenation naphthyl), norcamphyl, adamantyl, is particularly preferably cyclohexyl.This cycloalkyl can have the substituting groups such as more than 1 alkyl, cycloalkyl, halogen atom further.
Alternatively the group shown in two composition systems polycarboxylic acid anhydride of the alkyl of base, cycloalkyl, halogen atom and above-mentioned (1-1) is identical.
When r represents 2 ~ 8,2 R 14mutually can form divalent group by bonding, as this divalent group, such as, can enumerate and have or not there is substituent alkylidene group.
As the alkylidene group or do not have with substituent alkylidene group, be not particularly limited, such as, the alkylidene group of the carbonatoms 1 ~ 10 of straight-chain can be enumerated.Be preferably the alkylidene group of the carbonatoms 1 ~ 6 of the straight-chain such as methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, be preferably methylene radical or ethylidene.As this substituting group, with above-mentioned L 1in cited substituting group identical.
At this, x represents that more than 1, y represents that more than 1, x+y represents more than 2.As x+y, be preferably 2 ~ 150, be more preferably 4 ~ 100.X represents the mean number of the unit in polymkeric substance, is tried to achieve by gel permeation chromatography (GPC).
The arrangement of each unit of x and y is not defined in putting in order of the compound represented by general formula (6), compound represented by general formula (4) and the cyclohexane cyclohexanedimethanodibasic compound represented by general formula (7) can with block or random fashion copolymerization, the structural unit represented by general formula (1) and the structural unit represented by general formula (5) both can be each structural unit respectively continuously bonding also can be each structural unit alternately or randomly bonding.
The three component system polycarboxylic acid anhydride so obtained sometimes because of two alcohol radicals or two carboxyls sterie configuration and have the isomer of trans body and cis body, consider in being played making effect of the present invention, trans body, cis body and their mixture all can use.
The number-average molecular weight of three component system polycarboxylic acid anhydride of the present invention is preferably the scope of 500 ~ 6000, is more preferably the scope of 2000 ~ 6000.Number-average molecular weight such as can use the known methods such as gel permeation chromatography (GPC) to measure, as polystyrene conversion number-average molecular weight (Mn) and tried to achieve.
As the anhydride equivalent of three component system polycarboxylic acid anhydride of the present invention, be preferably the scope of 300 ~ 5000g/eq, be more preferably the scope of 500 ~ 3000g/eq, be particularly preferably the scope of 600 ~ 1500g/eq.It should be noted that, anhydride equivalent is applied the calculating formula recorded in embodiment described later and is calculated.
The volatility of three component system polycarboxylic acid anhydride of the present invention in the temperature range in order to make epoxy resin cure usually adopt is few.
Three component system polycarboxylic acid anhydride of the present invention is at 1790cm -1~ 1835cm -1scope in show the characteristic peak coming from anhydride group, particularly at 1800cm -1~ 1825cm -1scope in demonstrate characteristic peak.
2. the manufacture method of polycarboxylic acid anhydride
As long as the compound that the manufacture method of the polycarboxylic acid anhydride that the present invention relates to can obtain containing the structural unit represented by above-mentioned general formula (1) is just not particularly limited.Below, the manufacture method of the three component system polycarboxylic acid anhydride represented by the two composition systems polycarboxylic acid anhydride represented by above-mentioned (1-1) and (1-2) is described.
(2-1) manufacture method of two composition systems polycarboxylic acid anhydride
Of the present invention pair of composition system polycarboxylic acid anhydride such as manufactures as shown in following reaction formula-1.
[reaction formula-1]
(in formula, Rx, R 1~ R 10same as described above.)
Specifically, the manufacture method of of the present invention pair of composition system polycarboxylic acid anhydride possesses: make the diol compound represented by general formula (13) and the carboxylic acid anhydride represented by general formula (14) react and obtain the step (steps A) of the dicarboxylic acid compound represented by general formula (4); Condensation reaction is carried out thus the step (step B) of the compound of manufacture containing the structural unit represented by general formula (1) in the reaction solution containing obtained compound (4).
It should be noted that, the condensation reaction in above-mentioned steps B can be reacted under the existence of condensing agent.When carrying out reacting under the existence of condensing agent, as obtained polycarboxylic acid anhydride, produce the compound represented by general formula (3).
(in formula, Rx, R 1~ R 10, R 13same as described above with x.)
steps A
In steps A, the diol compound represented by general formula (13) and the carboxylic acid anhydride represented by general formula (14) are reacted, produces the dicarboxylic acid compound represented by general formula (4) thus.
The method that the reaction of steps A can adopt general glycol and carboxylic acid anhydride to react, is not particularly limited.
The reaction of steps A in suitable solvent or solvent-free under carry out.
When using solvent, as this solvent, such as, can enumerate: the aromatic hydrocarbons series solvents such as benzene,toluene,xylene; The halohydrocarbon series solvents such as methylene dichloride, chloroform, ethylene dichloride; The acid amides series solvents such as N-Methyl pyrrolidone (NMP), N,N-dimethylacetamide, DMF; The ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, 2-heptanone, dipropyl ketone, methyln-hexyl ketone, cyclopentanone, pimelinketone, methyl ethyl diketone; The glycol ethers series solvents such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dimethyl ether, propylene glycol methyl ether acetate: the ester such as gamma-butyrolactone, butylacetate series solvent; Their mixed solvent etc.Among these, particularly preferably pimelinketone or propylene glycol methyl ether acetate.
Relative to the glycol 1 mole represented by general formula (13), be generally 0 ~ 50 % by weight, be preferably 10 ~ 30 % by weight.
As the usage quantity of compound (14), suitably regulate, such as, relative to the glycol 1 mole represented by general formula (13), be generally 1.8 ~ 3 times moles, be preferably 2 ~ 2.2 times moles.
As the temperature of reaction in steps A, different because of the kind etc. of used starting compound, be not particularly limited, be preferably the scope of 50 ~ 150 DEG C, be more preferably the scope of 90 ~ 120 DEG C.
As the reaction times in steps A, different because of the kind, temperature of reaction etc. of used starting compound, be not particularly limited, be preferably the scope of 0.5 ~ 10 hour, be more preferably the scope of 1 ~ 5 hour.
step B
In step B, in the reaction solution containing the compound (4) obtained by steps A, carry out condensation reaction, manufacture polycarboxylic acid anhydride thus.
As the reaction of above-mentioned steps B, the general method making dicarboxylic acid generation condensation reaction can be adopted.
The reaction of step B in suitable solvent or solvent-free under carry out.
The kind of the solvent used in step B can from the solvent phase used in steps A with, also can be different.
When using solvent, as the usage quantity of solvent, suitably regulate, such as, relative to the dicarboxylic acid compound 1 mole represented by general formula (4), be generally 0 ~ 500 % by weight, be preferably 200 ~ 400 % by weight.
Condensation reaction in step B can be reacted under the existence of condensing agent, when carrying out reacting under the existence of condensing agent, as its condensing agent, such as, can enumerate: the carboxylic acid anhydride etc. such as diacetyl oxide, propionic anhydride, two (naphthenic acid) acid anhydride.Among these compounds, particularly preferably diacetyl oxide.
As the usage quantity of condensing agent, suitably regulate, such as, relative to the compound 1 mole represented by general formula (4), be generally 3 ~ 7 times moles, be preferably 3 ~ 4 times moles.
As concrete example, when using diacetyl oxide as condensing agent, in order to promote condensation reaction further, the preferred acetic acid distillation using carrying out with reaction as by product generation removes to reaction system outward while react.It should be noted that, when using solvent, can enumerate and drip above-mentioned cited solvent while make solvent distill the method removing and carry out condensation reaction together with the acetic acid generated as by product in reaction system.
As the temperature of reaction in step B, different because of the kind etc. of used starting compound, be not particularly limited, be preferably the scope of 50 ~ 150 DEG C, be more preferably the scope of 90 ~ 120 DEG C.
As the reaction times in step B, different because of the kind, temperature of reaction etc. of used starting compound, be not particularly limited, be preferably the scope of 0.5 ~ 20 hour, be more preferably the scope of 1 ~ 10 hour.
Step B can carry out or not carry out purifying and carry out continuously after step after by the compound purifying be obtained by reacting of above-mentioned steps A.
(2-2) manufacture method of three component system polycarboxylic acid anhydride
Three component system polycarboxylic acid anhydride of the present invention manufactures as shown in following reaction formula-2.
[reaction formula-2]
(in formula, Rx, R 1~ R 10, R 14same as described above with r.)
For three component system polycarboxylic acid anhydride of the present invention, such as, i) can be manufactured in compound (13), compound (14) and the disposable input reaction system of compound (7) (reaction formula-2) by step C and step D; Or ii) can also making after compound (13) and compound (14) react the step (steps A of reaction formula-1) first obtaining compound (4), to be manufactured by the step (step D) making obtained compound (4) and compound (7) react.
In step D, can react under the existence of condensing agent, when carrying out reacting under the existence of condensing agent, as obtained polycarboxylic acid anhydride, produce the compound represented by general formula (6).
(in formula, Rx, R 1~ R 10, R 13, R 14, r, x and y be same as described above.)
step C
In step C, diol compound represented by general formula (13) and the carboxylic acid anhydride represented by general formula (14) and the cyclohexane cyclohexanedimethanodibasic compound represented by general formula (7) are reacted, obtains the mixture of the dicarboxylic acid compound represented by general formula (4) and the cyclohexane cyclohexanedimethanodibasic compound represented by general formula (7).
The reaction of step C is that compound (13) first reacts with compound (14) and obtains the mixture of compound (4) and compound (7).
Therefore, can react making after the steps A shown in above-mentioned reaction formula-1 obtained compound (4) and compound (7).
The reaction of step C in suitable solvent or solvent-free under carry out.
The kind of the solvent used in step C can use the solvent shown in above-mentioned steps A.
When using solvent, as the usage quantity of solvent, suitably regulate, such as, relative to the dicarboxylic acid compound 1 mole represented by general formula (4), be generally 0 ~ 50 % by weight, be preferably 10 ~ 30 % by weight.
As temperature of reaction, different because of the kind etc. of used starting compound, be not particularly limited, be preferably the scope of 50 ~ 150 DEG C, be more preferably the scope of 90 ~ 120 DEG C.
As the reaction times, different because of the kind, temperature of reaction etc. of used starting compound, be not particularly limited, be preferably the scope of 0.5 ~ 10 hour, be more preferably the scope of 1 ~ 5 hour.
step D
In step D, make the dicarboxylic acid compound represented by general formula (4) and the cyclohexane cyclohexanedimethanodibasic compound represented by general formula (7) carry out condensation reaction, produce the polycarboxylic acid anhydride containing the structural unit represented by general formula (1) and the structural unit represented by general formula (5) thus.
As the reaction of step D, the general method making dicarboxylic acid generation condensation reaction can be adopted, in a solvent or solvent-free under carry out.The kind of the solvent used in step D can from the solvent phase used in step C with, also can be different.
When using solvent, as the usage quantity of solvent, suitably regulate, such as, relative to the dicarboxylic acid compound 1 mole represented by general formula (4), be generally 0 ~ 500 weight part, be preferably 200 ~ 400 weight parts.
Condensation reaction in step D can be reacted under the existence of condensing agent, when carrying out reacting under the existence of condensing agent, as its condensing agent, such as, can enumerate the carboxylic acid anhydride etc. such as diacetyl oxide, propionic anhydride, two (naphthenic acid) acid anhydride.Among these compounds, particularly preferably diacetyl oxide.
As the usage quantity of condensing agent, suitably regulate, such as, relative to the compound 1 mole represented by general formula (4), be generally 6 ~ 10 times moles, be preferably 6 ~ 8 times moles.
As concrete example, when using diacetyl oxide as condensing agent, in order to promote condensation reaction further, the preferred acetic acid distillation using carrying out with reaction as by product generation removes to reaction system outward while react.It should be noted that, when using solvent, can enumerate and drip above-mentioned cited solvent while make solvent distill the method removing and carry out condensation reaction together with the acetic acid generated as by product in reaction system.
The interpolation mol ratio of the cyclohexane cyclohexanedimethanodibasic class represented by above-mentioned general formula (7) and the compound represented by above-mentioned general formula (4) is preferably the scope of 0.1:99.9 ~ 70:30, is more preferably the scope of 10:90 ~ 55:45.
As temperature of reaction, different because of the kind etc. of used starting compound, be not particularly limited, be preferably the scope of 50 ~ 150 DEG C, be more preferably the scope of 90 ~ 120 DEG C.
As the reaction times, different because of the kind, temperature of reaction etc. of used starting compound, be not particularly limited, be preferably the scope of 0.5 ~ 20 hour, be more preferably the scope of 1 ~ 10 hour.
Step D can carry out or not carry out purifying and carry out continuously after step c after by the compound purifying be obtained by reacting of above-mentioned steps C.
The reaction of above-mentioned reaction formula-1 and reaction formula-2 can be carried out at ambient pressure, also or can add pressure and carries out in decompression.Atmosphere when implementing above-mentioned reaction only otherwise hinder reaction to be just not particularly limited, can be such as air atmosphere, nitrogen atmosphere, argon gas atmosphere etc. any one.In addition, above-mentioned reaction also can be undertaken by any one methods such as intermittent type, semibatch, continous ways.
The each compound obtained in above-mentioned reaction formula-1 and reaction formula-2 can by such as filtering reaction mixture, concentrating, extract, the separation method such as partial crystallization, recrystallization, column chromatography or the separation method that combines them carry out separation and purification.
Polycarboxylic acid anhydride of the present invention also can not carry out separation and purification and in the mode of the composition containing solvent for various uses.
epoxy curing agent
The epoxy curing agent that the present invention relates to contains above-mentioned polycarboxylic acid anhydride.
Although this polycarboxylic acid anhydride can be used alone as hardener for epoxy resin, optimal way makes this polycarboxylic acid anhydride and curing catalyst be mixed and made into solidifying agent used for epoxy resin and use.
In addition, the epoxy curing agent that the present invention relates to separately or can mix two or more and use.
The epoxy curing agent that the present invention relates to can use being dissolved under the state in solvent.In this case, in order to obtain good film, the concentration of polycarboxylic acid anhydride is preferably 5 ~ 60 % by weight, and further more preferably 10 ~ 50 % by weight.
composition epoxy resin
The composition epoxy resin that the present invention relates to contains (a) epoxy curing agent containing polycarboxylic acid anhydride, (b) epoxy resin and (c) curing catalyst.
Should (a) epoxy curing agent containing polycarboxylic acid anhydride be composition cited in above-mentioned " polycarboxylic acid anhydride ".
The composition epoxy resin that the present invention relates to can share (a) as required containing the known epoxy curing agent (such as, carboxylic-acid or its acid anhydrides) beyond the epoxy curing agent of polycarboxylic acid anhydride.
As (b) epoxy resin coordinated in the composition epoxy resin that the present invention relates to, known epoxy resin can be enumerated, be not particularly limited, such as, bisphenol A type epoxy resin can be exemplified, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, bisphenol-A epoxy resin, the diglycidyl ether-type epoxy resin of Hydrogenated Bisphenol A, Hydrogenated Bisphenol A D type epoxy resin, the diglycidyl ether-type epoxy resin of Hydrogenated Bisphenol A D, propylene glycol diglycidylether, the fatty family epoxy resin such as tetramethylolmethane polyglycidyl ether, the Triazine epoxy resin such as 1,3,5-tri-(2,3-epoxypropyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone, the epoxy resin formed by aliphatics or aromatic carboxylic acid and epoxy chloropropane, hetero ring type epoxy resin, containing the epoxy resin of volution, containing the acrylic resin of epoxy group(ing), the various epoxy resin such as epoxy modified resin.These epoxy resin can independent or appropriately combined two or more use.
As the epoxy resin of special recommendation, bisphenol A type epoxy resin, the diglycidyl ether-type epoxy resin of Hydrogenated Bisphenol A, bisphenol A type epoxy resin, 1,3,5-tri-(2 can be enumerated, 3-epoxypropyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones etc.
The anhydride group that this epoxy curing agent can exemplify (a) solidifying agent is the amount of the scope of 0.8 ~ 1.2 relative to the ratio [anhydride group/epoxide equivalent than] of the epoxy group(ing) 1 of (b) epoxy resin, is more preferably 0.9 ~ 1.1.
As (c) curing catalyst coordinated in the composition epoxy resin that the present invention relates to, known curing catalyst (curing catalysts) can be exemplified, such as triethylamine, N, the tertiary amine compounds such as N-dimethyl benzyl amine, DMA, three (dimethylamino methyl) phenol; The imidazolium compoundss such as 2-undecyl imidazole, 2-heptadecyl imidazole, 1-cyano ethyl-2-undecyl imidazole; The quaternary ammonium salts such as tetraethyl ammonium bromine salt, TBuA bromine salt; The organometallic compounds such as zinc acetate, sodium acetate, zinc octoate, stannous octoate, aluminium methyl ethyl diketone; The organophosphorus such as triphenylphosphine, triphenyl phosphite based compound etc.
These curing catalysts can independent or appropriately combined two or more use.Among these curing catalysts, preferred tertiary amine compound and organophosphorus based compound.
Relative to (b) epoxy resin 100 weight part, (c) curing catalyst in composition epoxy resin of the present invention can coordinate 0.1 ~ 5 weight part, is preferably 0.5 ~ 2 weight part.By coordinating the above curing catalyst of 0.5 weight part, condition of cure can be made to become shorter time.
Can other additives such as suitable combined with ultraviolet radiation absorption agent, antioxidant, photostabilizer, pigment, dyestuff, weighting agent, fire retardant, flowing regulator, flow agent, surface tension modifier, tackifier, coupling agent, defoamer, static inhibitor, solvent in the scope not hindering effect of the present invention as required in composition epoxy resin of the present invention.
When the additive using these optional, its usage quantity only otherwise hinder effect of the present invention to use in normally used scope, such as, relative to total 100 weight part of (a) solidifying agent, (b) epoxy resin and (c) curing catalyst, use in the scope below 10 weight parts.
Composition epoxy resin of the present invention can carry out mix and blend to manufacture to (a) of specified amount epoxy curing agent containing polycarboxylic acid anhydride, (b) epoxy resin and (c) curing catalyst and other additives etc. as required according to known method.
This epoxy curing agent, epoxy resin, curing catalyst and the disposable interpolation of each composition of other additives or can be divided into repeatedly can be added bit by bit.
Optional additive can when solidifying agent mixes with curing catalyst, add before epoxy resin, when adding epoxy resin or afterwards etc. add and mix arbitrary period.
Composition epoxy resin of the present invention is preferably the scope of 100 ~ 500 seconds at the gel time of 140 DEG C, is more preferably 200 ~ 400 seconds.
Resin combination of the present invention due to polycarboxylic acid anhydride self non-volatile, therefore coordinate when being heating and curing in the epoxy, the complex equilibrium of resin combination is also stablized.
epoxy resin molding
Epoxy resin molding (cured article) of the present invention is manufactured by the composition epoxy resin containing (a) epoxy curing agent containing polycarboxylic acid anhydride, (b) epoxy resin and (c) curing catalyst and other additives as required etc.
For the epoxy resin molding of the present invention so obtained, the high and molding (cured article) that initial stage transparent, heat-resisting xanthochromia, surface hardness, alkali resistance, solvent resistance, resistance to bend(ing) and adherence are excellent of second-order transition temperature (Tg) can be obtained.Therefore, the film being particularly suitable for needing to be cured at a relatively high temperature is formed.
Such as, as the method being manufactured film by composition epoxy resin of the present invention, can by being applied on matrix and make curing of coating be formed film that film, particularly thickness are below 1mm.The thickness of film is preferably about below 0.3mm.In addition, the lower value of the thickness of film is about 0.001mm usually.
As matrix, be not particularly limited, such as, can enumerate glass, pottery, aluminium, CCL (copper-clad lamination), thermotolerance polymeric membrane etc.
As method epoxy resin system: compositions of the present invention is applied on matrix, known method can be adopted with no particular limitation, such as, the known method such as silk screen printing, mould painting machine, comma coating machine, roller coating machine, scraping strip coating machine, gravure coater, curtain coater, Bracewell coater, air doctor blade formula coating machine, oppositely coating machine, dipping extrusion coating machine can be exemplified.
The curing of film is not particularly limited, and can adopt known method.In solidification, the known solidification equipments such as closed curing oven, the continuous tunnel furnace that can solidify continuously can be used.Heating can be undertaken by known methods such as hot air circulation, infrared heating, ratio-frequency heating.
Can be set as solidification value and set time about 120 ~ 200 DEG C of heating about 5 minutes ~ 5 hours.To be cured under the condition of about 10 minutes ~ 3 hours particularly preferably in about 120 ~ 180 DEG C.
The second-order transition temperature (Tg) of epoxy resin molding (cured article) of the present invention is preferably 80 ~ 200 DEG C, is more preferably 110 ~ 200 DEG C.Above-mentioned second-order transition temperature can pass through Differential Scanning Calorimetry (DSC method) and measure.
Transmissivity in the wavelength region may of epoxy resin molding (cured article) of the present invention preferably from visible ray to near-ultraviolet light is high.The initial stage transparency (YI) of epoxy resin molding of the present invention and at 150 DEG C the heat-resisting xanthochromia of thermal treatment after 5 days (Δ YI) spectral photometric colour measuring meter can be used (SPECTROPHOTOMETERCM-5 (Konica Minolta Opto Inc.'s system) measures, and is calculated by its reflectivity.
YI is expressed as the yellow chromaticity of body, and its value is less, and colorless transparency is more excellent, yellow chromaticity increases along with this value and increases.Δ YI represents degree, the i.e. heat-resisting xanthochromia of the xanthochromia through thermal history when, and the heat-resisting xanthochromia of the less then cured article of its value is better.
YI is preferably the scope of-0.5 ~ 3, is more preferably the scope of-0.5 ~ 2.Δ YI is preferably the scope of 0 ~ 4, is more preferably the scope of 0 ~ 3.5.
Epoxy resin molding (cured article) of the present invention is when measuring pencil hardness according to JISK5600-5-4 (version on April 20th, 1999), and pencil hardness is preferably more than HB, is more preferably more than H.
The alkali resistance of epoxy resin molding (cured article) of the present invention, solvent resistance, resistance to bend(ing) and adherence are good.
purposes
Epoxy curing agent of the present invention, epoxy resin molding or composition epoxy resin can be applied in the every field that can use thermosetting resin.Such as, tackiness agent, coating, ink, toning agent, coating-forming agent, shaped material (comprising sheet material, film, FRP etc.), electrically insulating material (comprising printed base plate, coating electric wire etc.), semiconductor-encapsulating material, anticorrosive additive material, softening agent, lubricating oil, fibre finish, tensio-active agent, medicine, agricultural chemicals etc. can be enumerated.
In addition, this epoxy resin molding due to the transparency, heat-resisting xanthochromia is excellent, therefore, it is possible to be suitable as the transparent hard-coating layer material of the such display unit of various glass substrate, trolley part, liquid crystal indicator or plasma display etc.For liquid crystal indicator, not easily because of the high heat of backlight, xanthochromia occurs very important, therefore composition epoxy resin of the present invention can be suitable as the coated material of liquid crystal indicator.So, epoxy resin molding of the present invention is also useful as indicating meter coated material.
[embodiment]
Embodiment and comparative example are below shown, the present invention is described in more detail, but the present invention is not defined in these.It should be noted that, the abbreviation of the compound in embodiment and comparative example is as described below.
The abbreviation > of < compound
[acid anhydrides]
リ カ シ ッ De HH: hexahydrophthalic anhydride (New Japan Chem Co., Ltd's system)
リ カ シ ッ De MH-T:4-methylhexahydrophthalic anhydride (New Japan Chem Co., Ltd's system)
リ カ シ ッ De HNA-100: the mixture (New Japan Chem Co., Ltd's system) of methyl bicycle [2.2.1] heptane-2,3-dicarboxylic anhydride and dicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride
[dicarboxylic acid compound]
CHDA:1,4-cyclohexane cyclohexanedimethanodibasic (New Japan Chem Co., Ltd's system)
[alcohols]
リ カ ビ ノ ー Le HB: Hydrogenated Bisphenol A (New Japan Chem Co., Ltd's system)
27-DH: decahydro-2,7-naphthalene glycol (Sugai chemical industry Co., Ltd. system)
Isosorbide-5-Nitrae-CHD:1,4-cyclohexanediol (Tokyo HuaCheng Industry Co., Ltd's system)
BHD:1,1-dicyclohexyl-4,4-glycol (Tokyo HuaCheng Industry Co., Ltd's system)
1,6-HD:1,6-hexylene glycol (Wako Pure Chemical Industries, Ltd.'s system)
BEPD:2-butyl-2-ethyl-1,3-PD (KH Xin Hua Co., Ltd. system)
NPG: neopentyl glycol (Mitsubishi Gas Chemical Co., Ltd's system)
CHDM:1,4-cyclohexanedimethanol (New Japan Chem Co., Ltd's system)
[solvent]
CHN: pimelinketone (NacalaiTesque Co., Ltd. system)
PGMEA: propylene glycol methyl ether acetate (KH Xin Hua Co., Ltd. system)
[epoxy resin]
JER828: bisphenol A type epoxy resin (Mitsubishi chemical Co., Ltd's system)
HBE-100: the diglycidyl ether-type epoxy resin (New Japan Chem Co., Ltd's system) of Hydrogenated Bisphenol A
[curing catalyst]
TBP-BB: tetrabutyl phosphorus bromine salt (Hokko Chemical Industry Co., Ltd.'s system)
[embodiment 1]
(1) in CHN15.0g, add リ カ ビ ノ ー Le HB17.6g (73.0mmol) and リ カ シ ッ De HH22.5g (146.0mmol, be 2.0 times mmols relative to リ カ ビ ノ ー Le HB), stir 3 hours in 110 DEG C under stream of nitrogen gas, thus obtain the CHN solution of dicarboxylic acid compound (HB/HH).
(2) in this dicarboxylic acid compound solution, add diacetyl oxide 26.1g (255.5mmol, be 3.5 times mmols relative to リ カ ビ ノ ー Le HB), stir 1 hour in 100 DEG C under stream of nitrogen gas.Then, 10.7 ~ 13.3kPa is decompressed to gradually by reaction vessel, then, CHN is dripped with the speed of 60ml/h in reaction vessel, on the other hand, acetic acid pair generated with the speed of 60ml/h distills removing to outside reaction system together with CHN, carries out condensation reaction simultaneously, obtain polycarboxylic acid anhydride solution of the present invention thus at 100 DEG C through 5 hours.Then, with CHN dilution, being adjusted to this polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 1.In addition, by following shown method, infrared absorption (FT-IR) spectrogram is measured to the polycarboxylic acid anhydride obtained in (2).
< infrared absorption (FT-IR) spectrogram >
By dry for the polycarboxylic acid anhydride solution for vacuum obtained in embodiment 1, distillation, except after desolventizing, obtains flaky solid polycarboxylic acid anhydride.Shown in Figure 1 by utilizing FT-IR to measure the spectrogram obtained for this polycarboxylic acid anhydride.
IR：2939cm -1、2861cm -1、1813cm -1、1722cm -1、1449cm -1、1299cm -1、1185cm -1、993cm -1
In Fig. 1, observe the peak (1813cm representing anhydride group -1), observe and obtain target polycarboxylic acid anhydride.
[embodiment 2]
Carry out similarly to Example 1 except リ カ ビ ノ ー Le HB17.6g (73.0mmol) is replaced with except 27-DH12.4g (73.0mmol), obtain polycarboxylic acid anhydride solution of the present invention.Then, with CHN dilution, being adjusted to this polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 1.In addition, after obtained polycarboxylic acid anhydride solution for vacuum is dry, distillation removes desolventizing, flaky solid polycarboxylic acid anhydride is obtained.Shown in Figure 2 by utilizing FT-IR to measure the spectrogram obtained for this polycarboxylic acid anhydride.
IR：2929cm -1、2861cm -1、1812cm -1、1722cm -1、1450cm -1、1300cm -1、1184cm -1、992cm -1
In Fig. 2, observe the peak (1812cm representing anhydride group -1), observe and obtain target polycarboxylic acid anhydride.
[embodiment 3]
In PGMEA15.0g, add リ カ ビ ノ ー Le HB13.3g (55.3mmol) and リ カ シ ッ De HH17.1g (110.6mmol, be 2.0 times mmols relative to リ カ ビ ノ ー Le HB), CHDA9.5g (55.3mmol, be 1.0 times mmols relative to リ カ ビ ノ ー Le HB), stir 3 hours in 110 DEG C thus obtain the PGMEA solution of dicarboxylic acid compound (HB/HH) under stream of nitrogen gas.In this dicarboxylic acid compound solution, add diacetyl oxide 39.5g (387.3mmol, be 7.0 times mmols relative to リ カ ビ ノ ー Le HB), stir 1 hour in 100 DEG C under stream of nitrogen gas.Then, 10.7 ~ 13.3kPa is decompressed to gradually by reaction vessel, then, in reaction vessel, CHN is dripped with the speed of 60ml/h, on the other hand, acetic acid pair generated with the speed of 60ml/h distills removing to outside reaction system together with CHN, carries out condensation reaction simultaneously, obtain polycarboxylic acid anhydride solution of the present invention thus at 100 DEG C through 5 hours.Then, with PGMEA dilution, being adjusted to this polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 1.In addition, after obtained polycarboxylic acid anhydride solution for vacuum is dry, distillation removes desolventizing, the polycarboxylic acid anhydride of flaky solid is obtained.Shown in Figure 3 by utilizing FT-IR to measure the spectrogram obtained for this polycarboxylic acid anhydride.
IR：2940cm -1、2861cm -1、1809cm -1、1722cm -1、1449cm -1、1300cm -1、1188cm -1、983cm -1
In Fig. 3, observe the peak (1809cm representing anhydride group -1), observe and obtain target polycarboxylic acid anhydride.
[embodiment 4]
Carry out similarly to Example 3 except リ カ ビ ノ ー Le HB13.3g (55.3mmol) is replaced with except 27-DH9.4g (55.3mmol), obtain polycarboxylic acid anhydride solution of the present invention.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 1.In addition, after obtained polycarboxylic acid anhydride solution for vacuum is dry, distillation removes desolventizing, the polycarboxylic acid anhydride of flaky solid is obtained.Measure utilizing FT-IR for this polycarboxylic acid anhydride the spectrogram obtained and be shown in Fig. 4.
IR：2934cm -1、2861cm -1、1808cm -1、1722cm -1、1450cm -1、1300cm -1、1186cm -1、983cm -1
In Fig. 4, observe the peak (1808cm representing anhydride group -1), observe and obtain target polycarboxylic acid anhydride.
[embodiment 5]
Carry out similarly to Example 3 except リ カ シ ッ De HH17.1g (110.6mmol) is replaced with except リ カ シ ッ De MH-T18.6 (110.6mmol), obtain polycarboxylic acid anhydride solution of the present invention.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 1.In addition, after obtained polycarboxylic acid anhydride solution for vacuum is dry, distillation removes desolventizing, the polycarboxylic acid anhydride of flaky solid is obtained.Measure utilizing FT-IR for this polycarboxylic acid anhydride the spectrogram obtained and be shown in Fig. 5.
IR：2946cm -1、2867cm -1、1809cm -1、1724cm -1、1451cm -1、1302cm -1、1201cm -1、987cm -1
In Fig. 5, observe the peak (1809cm representing anhydride group -1), observe and obtain target polycarboxylic acid anhydride.
[embodiment 6]
Carry out similarly to Example 3 except リ カ ビ ノ ー Le HB13.3g (55.3mmol) is replaced with except Isosorbide-5-Nitrae-CHD6.4g (55.3mmol), obtain polycarboxylic acid anhydride solution of the present invention.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 1.In addition, after obtained polycarboxylic acid anhydride solution for vacuum is dry, distillation removes desolventizing, the polycarboxylic acid anhydride of flaky solid is obtained.Measure utilizing FT-IR for this polycarboxylic acid anhydride the spectrogram obtained and be shown in Fig. 6.
IR：2942cm -1、2862cm -1、1807cm -1、1722cm -1、1450cm -1、1300cm -1、1183cm -1、983cm -1
In Fig. 6, observe the peak (1807cm representing anhydride group -1), observe and obtain target polycarboxylic acid anhydride.
[embodiment 7]
Carry out similarly to Example 6 except リ カ シ ッ De HH17.1g (110.6mmol) is replaced with except リ カ シ ッ De MH-T18.6g (110.6mmol), obtain polycarboxylic acid anhydride solution of the present invention.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 1.In addition, after obtained polycarboxylic acid anhydride solution for vacuum is dry, distillation removes desolventizing, the polycarboxylic acid anhydride of flaky solid is obtained.Measure utilizing FT-IR for this polycarboxylic acid anhydride the spectrogram obtained and be shown in Fig. 7.
IR：2948cm -1、2869cm -1、1808cm -1、1724cm -1、1452cm -1、1302cm -1、1188cm -1、986cm -1
In Fig. 7, observe the peak (1808cm representing anhydride group -1), observe and obtain target polycarboxylic acid anhydride.
[embodiment 8]
Carry out similarly to Example 3 except リ カ ビ ノ ー Le HB13.3g (55.3mmol) is replaced with except BHD11.0g (55.3mmol), obtain polycarboxylic acid anhydride solution of the present invention.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 1.
[embodiment 9]
Carry out similarly to Example 8 except リ カ シ ッ De HH17.1g (110.6mmol) is replaced with except リ カ シ ッ De MH-T18.6g (110.6mmol), obtain polycarboxylic acid anhydride solution of the present invention.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 1.In addition, after obtained polycarboxylic acid anhydride solution for vacuum is dry, distillation removes desolventizing, the polycarboxylic acid anhydride of flaky solid is obtained.Measure utilizing FT-IR for this polycarboxylic acid anhydride the spectrogram obtained and be shown in Fig. 8.
IR：2943cm -1、2862cm -1、1809cm -1、1723cm -1、1452cm -1、1302cm -1、1193cm -1、987cm -1
In Fig. 8, observe the peak (1809cm representing anhydride group -1), observe and obtain target polycarboxylic acid anhydride.
[comparative example 1]
1 is added in PGMEA15.0g, 6-HD11.1g (93.9mmol) and リ カ シ ッ De HH29.0g (187.8mmol, relative to 1,6-HD is 2.0 times of mmol), stir 3 hours in 110 DEG C thus obtain the PGMEA solution of dicarboxylic acid compound (1,6-HD/HH) under stream of nitrogen gas.Add diacetyl oxide 33.6g (328.7mmol, be 3.5 times mmols relative to 1,6-HD) to this dicarboxylic acid compound solution, stir 1 hour in 100 DEG C under stream of nitrogen gas.Then, 10.7 ~ 13.3kPa is decompressed to gradually by reaction vessel, then, in reaction vessel, CHN is dripped with the speed of 60ml/h, on the other hand, acetic acid pair generated with the speed of 60ml/h distills removing to outside reaction system together with CHN, carries out condensation reaction simultaneously, obtain polycarboxylic acid anhydride solution thus at 100 DEG C through 5 hours.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 2.
[comparative example 2]
Carry out in the same manner as comparative example 1 beyond 1,6-HD11.1g (93.9mmol) being replaced with BEPD15.0g (93.9mmol), obtain polycarboxylic acid anhydride solution.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 2.
[comparative example 3]
Carry out in the same manner as comparative example 1 beyond 1,6-HD11.1g (93.9mmol) being replaced with NPG9.8g (93.9mmol), obtain polycarboxylic acid anhydride solution.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 2.
[comparative example 4]
Carry out in the same manner as comparative example 1 beyond 1,6-HD11.1g (93.9mmol) being replaced with CHDM13.5g (93.9mmol), obtain polycarboxylic acid anhydride solution.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 2.
[comparative example 5]
Carry out in the same manner as comparative example 4 except リ カ シ ッ De HH29.0g (187.8mmol) is replaced with except リ カ シ ッ De MH-T31.6g (187.8mmol), obtain polycarboxylic acid anhydride solution.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 2.
[comparative example 6]
1 is added in PGMEA15.0g, 6-HD7.9g (66.8mmol) and リ カ シ ッ De HH20.6g (133.6mmol, relative to 1,6-HD is 2.0 times of mmol), CHDA11.5g (66.8mmol, relative to 1,6-HD is 1.0 times of mmol), stir 3 hours in 110 DEG C thus obtain the PGMEA solution of dicarboxylic acid compound (1,6-HD/HH) under stream of nitrogen gas.In this dicarboxylic acid compound solution, add diacetyl oxide 47.7g (467.6mmol, be 7.0 times mmols relative to 1,6-HD), stir 1 hour in 100 DEG C under stream of nitrogen gas.Then, 10.7 ~ 13.3kPa is decompressed to gradually by reaction vessel, then, in reaction vessel, CHN is dripped with the speed of 60ml/h, on the other hand, acetic acid pair generated with the speed of 60ml/h distills removing to outside reaction system together with CHN, carries out condensation reaction simultaneously, resulting in polycarboxylic acid anhydride solution at 100 DEG C through 5 hours.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 2.
[comparative example 7]
Carry out in the same manner as comparative example 4 beyond 1,6-HD7.9g (66.8mmol) being replaced with BEPD10.7g (66.8mmol), obtain polycarboxylic acid anhydride solution.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 2.
[comparative example 8]
Carry out in the same manner as comparative example 4 beyond 1,6-HD7.9g (66.8mmol) being replaced with NPG7.0 (66.8mmol), obtain polycarboxylic acid anhydride solution.Then, with PGMEA dilution, Setup Cost polycarboxylic acid anhydride is 40 % by weight.Use the polycarboxylic acid anhydride solution obtained, evaporation rate when mensuration number-average molecular weight, heating and anhydride equivalent.The results are shown in table 2.
[comparative example 9 ~ 11]
Measure リ カ シ ッ De HH (comparative example 9), リ カ シ ッ De MH-T (comparative example 10), リ カ シ ッ De HNA-100 (comparative example 11) heating time evaporation rate.The results are shown in table 2.
< number-average molecular weight >
Polycarboxylic acid anhydride solution is about 0.1g tetrahydrofuran (THF) 2ml to dissolve, prepares molecular weight determination sample solution.Number-average molecular weight Mn uses gel permeation chromatography (GPC) to obtain the number-average molecular weight (Mn) of polystyrene conversion with following condition determination.
[condition determination]
Device: pump (the LC-20AD type that Shimadzu Scisakusho Ltd manufactures), post (ShodexKF-801, ShodexKF-802, ShodexKF-804, is Showa Denko K. K's system), detector (Shimadzu Scisakusho Ltd manufacture RID-10A type)
Elutriant: tetrahydrofuran (THF)
Column temperature 40 DEG C, flow 1.0mL/ minute
Evaporation rate > during < heating
By polycarboxylic acid anhydride solution 120 DEG C, under the decompression of 0.7kPa through 30 ~ 40 minutes completely distillation except desolventizing.In the diameter metal ware that is 40mm, measure the polycarboxylic acid anhydride 0.10g obtained after distillation removing, heat 1 hour at 180 DEG C, according to the weight change determination evaporation rate before and after heating.Evaporation rate is applied following calculating formula (1) and is calculated.
Evaporation rate (%)=(W 2-W 1) × 100/W 1(1)
W 1: the weight (g) of the polycarboxylic acid anhydride before heating
W 2: the weight (g) of the polycarboxylic acid anhydride after heating
< anhydride equivalent >
In Erlenmeyer flask, measure 3.00g polycarboxylic acid anhydride solution, add pyridine 10ml and dissolve.After further interpolation ion exchanged water 50ml carries out 3 hours reflux, naturally cool to room temperature (25 DEG C).After naturally cooling, add 51 % by weight phenolphthalein solutions, utilize 0.5M potassium hydroxide-ethanol solution to carry out titration, be set to terminal with the point developed the color lasting 30 seconds.Anhydride equivalent is applied following calculating formula (2) and is calculated.Anhydride equivalent (g/eq) is the value of the quality gram to represent the polycarboxylic acid anhydride solution containing 1 mole of anhydride group.
Anhydride equivalent=(B × 2 × 10 3)/(A × N) (2)
A: the 0.5M potassium hydroxide-ethanol solution (ml) used in titration
B: sample collection amount (g)
N: the equivalent concentration (Regulations spends surely) of potassium hydroxide-ethanol solution
[embodiment 10 ~ 19]
The polycarboxylic acid anhydride solution obtained in embodiment 1 ~ 9 is mixed with the ratio of components (weight part) shown in table 3 with epoxy resin and curing catalyst, obtains Epoxy resin composition solution.Use the Epoxy resin composition solution obtained, measure gel time, second-order transition temperature, the initial stage transparency, heat-resisting xanthochromia, surface hardness, alkali resistance, resistance to NMP, resistance to bend(ing) and adherence.The results are shown in table 3.
[comparative example 12 ~ 20]
The polycarboxylic acid anhydride solution obtained in comparative example 1 ~ 8 or MH-T are mixed with the ratio of components (weight part) shown in table 4 with epoxy resin and curing catalyst, obtains Epoxy resin composition solution.Use the Epoxy resin composition solution obtained, measure gel time, second-order transition temperature, the initial stage transparency, heat-resisting xanthochromia, surface hardness, alkali resistance, resistance to NMP, resistance to bend(ing) and adherence.The results are shown in table 4.
< gel time >
According to JISC2161-B (version on March 23rd, 2010), the solution of several drip ring epoxy resin composition that the metal sheet being adjusted to 140 DEG C drips, during with wire touching composition surface, be measured to the time (second) till pulling out silk between composition and wire.
< second-order transition temperature >
The diameter inflow of the solution of composition epoxy resin being equipped with aluminium foil is about in the metal ware of 4cm and makes the thickness after solidification be 100 μm, at 100 DEG C by solvent seasoning 10 minutes, 130 DEG C of solidifications 2 hours.This cured article is peeled off from aluminium foil, uses means of differential scanning calorimetry device (DSC6220 (SIINanoTechnology Inc.)), by flex point when measuring using following condition determination as second-order transition temperature (DEG C).
Condition determination: heat up from-20 DEG C with 20 DEG C/min, measures and is performed until 180 DEG C
The < initial stage transparency (YI) and heat-resisting xanthochromia (Δ YI) >
For the cured article that the thickness produced with the method same with the test film of second-order transition temperature is 100 μm, under the state that one side is adhesive with above-mentioned aluminium foil, (SPECTROPHOTOMETERCM-5 (Konica Minolta Opto Inc.'s system) measures reflectivity to use spectral photometric colour measuring meter.Calculate YI according to reflectivity to carry out according to the regulation of ASTMD1925-70 (Reapproved1988).Measure the YI before cured article is heat-treated and the YI after carrying out thermal treatment in 5 days at 150 DEG C, by both differences as heat-resisting xanthochromia (Δ YI).YI represents the yellow chromaticity of cured film, and the less then colorless transparency of its value is more excellent, and yellow chromaticity increases along with this value and increases.Δ YI represents degree, the i.e. heat-resisting xanthochromia of the xanthochromia when subjected to thermal history, and the heat-resisting xanthochromia of the less then cured article of this value is better.
< surface hardness >
Be on the steel plate of 300 μm in thickness by the solution coat of composition epoxy resin, at 100 DEG C by solvent seasoning 10 minutes, then produce 130 DEG C of solidifications 2 hours the cured coating film that thickness is 30 μm.Use Pencil scratch to this cured coating film chart surface hardness according to JISK5600-5-4 (version on April 20th, 1999).That is, have on the steel plate carrying out the cured coating film measured, the load applying 1kg the angles of 45 degree from above makes pencil scratch about 10mm, confirms the situation producing scar.To the hardness of the hardest pencil of scar do not produced as surface hardness.
< alkali resistance >
Use the cured coating film that the method same with surface hardness mensuration test film is produced, under 25 DEG C of environment, the NaOH aqueous solution of 5 % by weight concentration is dripped on the cured coating film on steel plate.Rinsed with water after 30 minutes, dripped the change of the outward appearance at position by visual observations evaluation.Its benchmark evaluated is as described below.
Zero: unconfirmed to change on the surface of cured coating film.
×: confirm change on the surface of cured coating film.
The resistance to NMP > of <
Use the cured coating film that the method same with surface hardness mensuration test film is produced, under 25 DEG C of environment, use METHYLPYRROLIDONE (NMP), the resistance to NMP of the method evaluation recorded in the item by above-mentioned alkali resistance.Its metewand is as described below.
Zero: unconfirmed to change on the surface of cured coating film.
×: confirm change on the surface of cured coating film.
< resistance to bend(ing) >
Use the cured coating film that the method same with surface hardness mensuration test film is produced, by steel plate bending 180 °, evaluated the state of the cured coating film of bending part by visual observations.Its metewand is as described below.
Zero: outward appearance is unconfirmed to change.
×: outward appearance confirms floats (floating I), stripping.
< adherence >
Use the cured coating film that the method same with surface hardness mensuration test film is produced, according to JISK5600-5-6 (version on April 20th, 1999), cross cut test test is carried out to the cured coating film on steel plate, evaluates by visual observations the state that cellophane tape peels off the cured coating film caused.Its metewand is as described below.
Zero: unconfirmed to cured coating film stripping.
×: confirming cured coating film has stripping.
[table 1]
[table 2]
[table 3]
[table 4]
Result according to above-mentioned table 1 ~ 4 is known as below content.
The polycarboxylic acid anhydride obtained in embodiment 1 ~ 9 and comparative example 1 ~ 8 does not almost volatilize when heating, compared with the acid anhydrides (evaporation rate during heating is more than 90%) in the past such as the HH shown in comparative example 9 ~ 11, obvious non-volatile excellent.
For the Epoxy resin composition solution obtained in embodiment 10 ~ 19, the physical property of its cured article does not reduce, obtain stable physical property, obtain thermotolerance (Tg), the transparency, heat-resisting xanthochromia excellent and meet the resin molded body of surface hardness, solvent resistance, resistance to bend(ing) and adherence simultaneously.
For the Epoxy resin composition solution obtained in comparative example 12 ~ 20, show the result of low, the heat-resisting xanthochromia difference of second-order transition temperature of its cured article.When the use acid anhydrides in the past (MH-T) of comparative example 20 is as solidification compound, known when resin is heating and curing acid anhydrides volatilize, only have the loss of an acid anhydrides part in solidification compound, the complex equilibrium of resin is disintegrated thus, can not obtain desired solidification physical property.Therefore, think and be not suitable for indicating meter transparent coating material purposes etc.
In contrast to this, the polycarboxylic acid anhydride of the present application owing to having above-mentioned excellent effect, therefore, it is possible to be suitable for indicating meter transparent coating material purposes etc.
Utilizability in industry
The present invention relates to the polycarboxylic acid anhydride containing the structural unit represented by following general formula (1).
Polycarboxylic acid anhydride of the present invention does not have volatility, when therefore such as using the solidifying agent of this polycarboxylic acid anhydride as epoxy resin, the complex equilibrium of resin combination is stablized, and therefore can obtain the resin molded body that thermotolerance, the transparency, heat-resisting xanthochromia, surface hardness, solvent resistance, resistance to bend(ing) and adherence are excellent.Polycarboxylic acid anhydride of the present invention has performance excellent like this, therefore, it is possible to industrially use in field widely.Particularly can be suitable as the coated material of indicating meter.

Claims (15)

1. a polycarboxylic acid anhydride, it contains the structural unit represented by general formula (1),
In formula, Rx represents cycloalkylidene or more than 2 cycloalkylidenes group via singly-bound or divalent group bonding, and at this, this cycloalkylidene has or do not have substituting group,
R 1~ R 10identical or different, represent hydrogen atom respectively or have or not there is substituent alkyl, R 1~ R 10among, two groups can form divalent group by bonding mutually.
2. polycarboxylic acid anhydride as claimed in claim 1, wherein, the divalent group of Rx represented by general formula (2),
In formula, W 1and W 2identical or different, represent and have or not there is substituent cycloalkylidene,
L 1represent singly-bound, have or not there is substituent alkylidene group, have or not there is substituent cycloalkylidene, there is or do not have substituent ring alkylidene ,-O-,-S-,-CO-,-SO-or-SO 2-, n represents the integer of 0 or 1, and wavy line represents bonding position.
3. polycarboxylic acid anhydride as claimed in claim 2, wherein, W 1and W 2identical or different, be selected from the divalent group represented by following general formula (a) or (b),
In formula, R 11and R 12identical or different, represent respectively and there is or do not have substituent alkyl or have or not there is substituent cycloalkyl,
O represents the integer of 0 ~ 8, when o represents 2 ~ 8, and 2 ~ 8 R 11identical or different, when o represents 2 ~ 8,2 R 11mutually can form divalent group by bonding,
P represents the integer of 0 ~ 12, when p represents 2 ~ 12, and 2 ~ 12 R 12identical or different, when p represents 2 ~ 12,2 R 12mutually can form divalent group by bonding, wavy line represents bonding position.
4. polycarboxylic acid anhydride as claimed in claim 1, wherein, the compound of the polycarboxylic acid anhydride containing the structural unit represented by general formula (1) represented by general formula (3),
In formula, Rx and R 1~ R 10same as described above, R 13represent and have or do not have substituent alkyl or have or do not have substituent cycloalkyl, x represents more than 2.
5. a manufacture method for polycarboxylic acid anhydride according to claim 1, it possesses the step of carrying out condensation reaction in the reaction solution containing the compound represented by general formula (4),
In formula, Rx and R 1~ R 10same as described above.
6. a polycarboxylic acid anhydride, it is obtained by manufacture method according to claim 5.
7. a polycarboxylic acid anhydride, it contains the structural unit represented by general formula (1) and the structural unit represented by general formula (5),
In formula, Rx represents cycloalkylidene or more than 2 cycloalkylidenes group via singly-bound or divalent group bonding, and at this, this cycloalkylidene has or do not have substituting group,
R 1~ R 10identical or different, represent hydrogen atom respectively or have or not there is substituent alkyl, R 1~ R 10among, two groups can form divalent group by bonding mutually,
In formula, R 14identical or different, represent respectively and have or do not have substituent alkyl or have or do not have substituent cycloalkyl, r represents the integer of 0 ~ 8, when r represents 2 ~ 8, and 2 ~ 8 R 14identical or different, when r is 2 ~ 8,2 R 14mutually can form divalent group by bonding.
8. polycarboxylic acid anhydride as claimed in claim 7, wherein, the divalent group of Rx represented by general formula (2),
In formula, W 1and W 2identical or different, represent and have or not there is substituent cycloalkylidene, L 1represent singly-bound, have or not there is substituent alkylidene group, have or not there is substituent cycloalkylidene, there is or do not have substituent ring alkylidene ,-O-,-S-,-CO-,-SO-or-SO 2-, n represents the integer of 0 or 1, and wavy line represents bonding position.
9. polycarboxylic acid anhydride as claimed in claim 8, wherein, W 1and W 2identical or different, be selected from the divalent group represented by following general formula (a) or (b),
In formula, R 11and R 12identical or different, represent respectively and there is or do not have substituent alkyl or have or not there is substituent cycloalkyl,
O represents the integer of 0 ~ 8, when o represents 2 ~ 8, and 2 ~ 8 R 11identical or different, when o represents 2 ~ 8,2 R 11mutually can form divalent group by bonding,
P represents the integer of 0 ~ 12, when p represents 2 ~ 12, and 2 ~ 12 R 12identical or different, when p represents 2 ~ 12,2 R 12mutually can form divalent group by bonding, wavy line represents bonding position.
10. polycarboxylic acid anhydride as claimed in claim 7, wherein, the compound of polycarboxylic acid anhydride represented by general formula (6) containing the structural unit represented by general formula (1) and the structural unit represented by general formula (5),
In formula, Rx, R 1~ R 10, R 14same as described above with r, R 13represent and have or do not have substituent alkyl or have or do not have substituent cycloalkyl, x represents that more than 1, y represents that more than 1, x+y represents that the arrangement of each unit of more than 2, x and y is not defined in the order of above-mentioned arrangement.
The manufacture method of 11. 1 kinds of polycarboxylic acid anhydrides according to claim 7, it possesses the step of carrying out condensation reaction in the reaction solution containing the compound represented by general formula (4) and the cyclohexane cyclohexanedimethanodibasic compound represented by general formula (7),
In formula, Rx and R 1 ~r 10it is same as described above,
In formula, R 14same as described above with r.
12. 1 kinds of polycarboxylic acid anhydrides, it is obtained by manufacture method according to claim 11.
13. 1 kinds of epoxy curing agents, it contains Claims 1 to 4, polycarboxylic acid anhydride according to any one of 6 ~ 10,12.
14. 1 kinds of compositions, it contains (a) epoxy curing agent according to claim 13, (b) epoxy resin and (c) curing catalyst.
15. 1 kinds of moldinies, it obtains by making composition according to claim 14 solidify.
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